Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resin salts



United States Patent PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN AMlNE-MODI- FIED THERMOPLASTIC PHENOL-ALDEHYDE RESIN SALTS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, 'Del., a corporation of Delaware No Drawing. Application January 2, 1953, Serial No. 329,482

18 Claims. (C1, 252-341) The present invention is a continuation-in-part of my two co-pending applications, Serial No. 288,742, filed May 19, 1952, now abandoned, and Serial No. 296,083, filed June 27, 1952, now U. 8. Patent 2,679,484.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

My aforementioned co-pending application, Serial No. 296,083, filed June 27, 1952, is concerned with a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including certain amino resin condensates therein described.

My present invention is concerned with demulsification which involves the use of the aforementioned amino resin condensate in the form of a gluconic acid salt, i. e., a form in which all the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

Needless to say, :all that is required is to prepare the amine resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products go for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufiicient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsific-ation using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all or part of the basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene 1n the emulsification test includes such obvious Variant.

For convenience, what is said hereinafter will be divided into six parts:

Part 1 is concerned with the general structure of the amine-modified resins which are converted into the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary amines free from a hydroxyl radical which may be employed in the preparation of the herein described aminemodified resins;

Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds which are neutralized subsequently with gluconic acid;

Part 5 is concerned with the conversion of the basic condensate into the corresponding salt of gluconic acid; and

Part 6 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts.

PART 1 The compounds herein described and particularly useful as demulsifying agents are gluconic acid salts of heatstable oxyalkylationesusceptible resinous condensation products of certain phenol-aldehyde resins, basic nonhydroxylated secondary monoamines and formaldehyde described in applications Serial Nos. 288,742 and 296,083 to which reference is made for a discussion of the general structure of such resins.

These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an effort to present certain resin structure. would be the following:

Such formula R R n R in which R represents any appropriate hydrocarbon nadical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, Which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholine and piperidine. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3- to 6 phenolic nuclei Patented Nov. 20, 1956 as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be .a counterbalancing'hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional fromthe standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difu'nctional radical to a trifnnctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one may prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat-stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

Whathas been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to 140 to 150'C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumptionthat generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heatreactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process employed in the manufacture of the condensation product is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces.

methylol groups attached to'the phenolic nuclei which, in turn, react with the amine. vIt would be immaterial, of

course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different moleculesare simultaneously involved although,

for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART '2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble,

water-insoluble resin polymers of a composition approximated in an idealized form by the formula alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from' formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less. I

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, suchas benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are, xylene or benzene-soluble as described in aforementioned U. S.-

Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

, If one selected a resin of the kind just described pre-' viously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized oversimplification previously referred to, the resultant product might be illustrated thus:

R OH 0.1 OH R H H H H H ii ii I R R R R nR The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place.- For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule,-or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, asindicated' in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is Well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all- It is preferable that the resins employed be substantially neutral. In other words, if prepared by'using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in' practically every case is to have the resin neutral.

In preparing resins one does not get a single'polymer, i. e., one having just 3 units, or just 4 units, or just 5 poses of convenience suitable resins are characterized the following table:

TABLE I M01. wt. EX- R!!! of resin ample R Position derived 1!. molecule number of R from (based on n+2) Phenyl Para. Formal- 3. 5 992. 5

dehyde. don..." 3. 5 882. 5 .d0 3. 5 882.5 .do. 3. 5 1, 025. 5 Tertiary amyl do. 3. 5 959.5 Mixed secondary .do. 3.5 805.5

and tertiary amyl. Propyl do 3. 5 805. 5 Tertiary hexyl do 3. 5 1, 036. 5 Oetyl do a. 5 1,190.5 do 3.5 1,267.5

do. a. 5 1,344. 5 I y do 3. 5 1, 49s. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1,022.5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071.5

Tertiary amyl 3. 5 1, 148. 5 Nonyl 3. 5 1, 456. 5 Tertiary butyl 3. 5 1, 008.5

Tertiary amyl 1. 3. 5 1, 085.5 onyl .1 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1, 083. 4 I l 4. 2 1, 430. 6 4. 8 1, 094. 4 4. 8 1,189.6 4. s 1, 570. 4 1. 5 604. 0 1. 5 646. 0 1.5 653.0 1 1. 5 688. 0

Amyl 2. 0 692.0 390 Hexyl 2.0 748. 0 40a Cy o-hexyl do 2.0 740. 0

PART 3 As has been pointed out previously, the amine herein employed as a reactant is a basic secondary monoamine,

and preferably a strongly basic secondary monoamine, free from hydroxyl groups whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, .dioctylamine, and di-- n-onylamine. Other amines include bis(1,3-dimethylbutyl)arnine. There are, of course, a variety of primary 'zylamine itself, to produce a suitable reactant. Needless to say, one can use secondary arnines,.such as dicyclohexylamine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl' group and one alkyl group, such as ethylcyclohexyl amine, ethylbenzylamine, etc.

Another class of amines which are particularly desirl able for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula [R CnHZn) ziq /N}I l l in which x is a small whole number having a value of l or more, and may be as much as or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to l, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944, to Spence. The'latter patent describes typical haloalkyl ethers such as (31330 C2H4C1 GE -CH2 Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also 'can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Compounds so obtained are exemplified by C2H4OC2H4O C2H4) 2NH (CBH17OC2H4OCZH4OC2II4)VZNH C4H9OCH2CH (CH3 0 (CH3 CHCHz zNI-I (CHaOCHzCHzOCHaCI-IzOCHzCI-Iz)zNH CH3OCH2CH2CH2CH2CH2CH2) zNH Other somewhat similar secondary amines are those of the composition R-O(CH2)3 R o (cum as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained'frorn products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phen'oxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by 8 PART 4 The products obtained by the herein described processes employed in the manufacture of the condensation product represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself The condensation of the resin, the amine and formalde hyde is described in detail in applications Serial Nos. 288,742 and 296,083, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with anequal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C., and 146 grams of diethylamine added. 7

The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution'and 162 grams were employed, which were added in about 2%. hours. and kept within a temperature range of 30 to 45 C. for about 20 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time, and the presence of unreacted formaldehyde noted.

odor of formaldehyde was no longer detectable the phaseseparating trap was set so as to eliminate all water of solution and reaction. After the-water was eliminated part of the xylene was removed until the temperature reached approximately C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction "stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. In other examples it varied from 24 hours to 36 hours. Time can be reduced by cutting lowtemperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the Water, both the solution and condensation. ,After all the water had been separated enough xylene was taken out to have the final prod- The following example will serve The mixture was stirred vigorously uct reflux" for several hours'somewhere in the range of 10 cedurerdepends on? the .faritcthatcth-e phase s'eparating. trap can be used but it is 'preferableto stayibelow 150C. so as to avoid any possibledecomposition.-

The xylene solution of the-condensate, as previously Note that as pointed out previously, this procedure is :described, is subjected to vacuum distillation so asv to illustrated by 24 examples in Table II.

remove about one-half the xylene. Approximately two- TABLE 11 Strength of Reac- Reac- Max.

Ex. Resin Amt., Amine used and amount tormalde- Solvent used tion tion distill No. used grs. hyde soln. and amt. temp., time, temp.,

and amt. 0. hrs. 0.

882 Diethylamine, 146 grams 37%, 162 g Xylene, 882 g..' 20-25 30 150 480 Diethylamine, 73 grams... 37%, 81 gm. .Xylene, 480 g ,22-30' 24 152 033 d0 30%, 100 g Xylene, 633 g. 21-24 38 147 Dlbutylamine, 129 grams 37%, 81 g Xylene, 441 g 25-37 32 149 do do Xylene, 480 gm. 20-24 35 149 ..d0. Xylene, 633 g 18-23 24 150 37%, 162 g... Xylene, 882 g 20-26 35 145 37%, 81 g.-.. Xylene, 480 gm. 19-27 24 156 do Xylene, 633g. 24 147 0%, Xylene, 473 g 38 148 d Xylene, 511 30 146 37%, 81 Xylene, 665 24 150 30%, 100 g... .Xylene, 441 g 20-22 31 147 "d Xylene, 480 g. 20-24 36 148 37%, 81 g Xylene, 595 g 23-28 145 (04110001120151 (OH;)O(CH3)CHCH1)1NH, 361 grams. do Xylene, 441 gm. 21-23 24 151 (C4H9OCH2OH(GH3)O(CH3)OHCH2)ZNH,361gISJIIS do Xylene, 480 g 20-24 24 150 511 (0.4119001320116113)O(OH )CHCH)2NE, 361 grams. 100 g... Xylene, 511 g 20-22 25 146 498 (CEsOoHgoHzoCHzCHzOOHzCHz)zNH, 309 grams 37%, 81 g Xylene, 498 g 20-25 24 140 542 (C33003201120CH2CHZOCHZCH2 2NH, 309 grams do Xylene, 542 g 28-38 30 142 547 (CH30CHZCH2OOHZCHZOCHZCH2)2NH, 309 grams do Xylene, 547 g 25-30 26 148 441 (CHQOCH2CH2CH2CH2CH2CH2)2NH, 245 grams do Xylene, 441 g 20-22 28 143 505 (CHQOOHZCH2OH2CH2OH2OH2)2NH, 245 grams 0%, 100 g". Xylene, 595 18-20 25 146 391 (C1130OHgCHzCHzCHzOI-I2CH2)2NH, 98 grams 30%, 50 g Xylene, 391 g 19-22 24 145 PART 5 The conversion of the basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensates invariably contain more than two basic nitrogen atoms. One can neutralize either one, or both, basic nitrogen atoms.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, at least not of the salts of the herein described condensates. Such salts appear to be stable, or stable for all practical purposes, at temperatures slightly above the boiling point of water and perhaps at temperatures as high as 150 C. or thereabouts.

For reasons pointed out previously, it is most convenient to handle the condensate as a solution, generally a solution in an inexpensive solvent, such as benzene, xylene, an aromatic petroleum solvent, or the like. A number of the condensates previously described have been prepared in 50% solution as noted. Adding the calculated stoichiometric amount of 50% gluconic acid, calculated on the basis of the theoretical basic nitrogen atoms present, forms such salt which, in many instances may be slightly on the basic side and in other instances perhaps slightly on the acid side. The salt formation is merely a matter of agitating at room temperature, or somewhat higher temperature if desired, particularly under a reflux condenser. After salt formation is complete, I have permitted the solution to stand for about 6 to 72 hours.

Sometimes, depending on the composition, there is some separation of an aqueous phase. On a laboratory scale,

this procedure is conducted in a separatory funnel. If

thirds of the xylene removed is replaced by benzene. This mixed solvent combination is subjected to refluxing action under a condenser with aphase-separatin'g trap. With the distillation point adjusted so as to be somewhere between to C. the mixture is refluxed and the water separated. If it is not within-this range more benzene is added or, if need, be, a little more xylene is added to bring it within the range. By this method the phase-separating trap eliminates the water. The temperature at all times is left below C. At the end of the separation a suitable amount of solvent is added, or eliminated, by distillation so as to yield a solution of predetermined concentration, for instance, 50%., Using a somewhat similar procedure one can obtain the solvent-free material by merely subjecting the xylene solution of the condensate to vacuum distillation so as to remove all the xylene. The condensate itself is perfectly stable at C. or thereabouts and, thus, there is no particular danger of degradation involved in this step. The solvent-free material is then dissolved in benzene instead of xylene and water eliminatedin the manner previously described. The benzene is eliminated by vacuum distillation in such a way thatythe temperature never gets above 135 C. or 140 C." Actually, with care the solution previously described, to wit, the xylene-benzene solution, also can be removed without decomposition.

The solution of the salts varies in color from reddisharnber to deep red or deep amber. Needless to say, if the condensateitself has been bleached by means of char, filtering clays, or the like, then the condensate salt is practically water-white or has a pale straw color. If desired, the solution of the salt can be bleached in a similar manner using filter chars, bleaching clays, or the like. From a practical standpoint I have found no reason to decolorize the materials, or to prepare then in any other than a solution form, using the cheapest solvents. This applies particularly when this material is used as a demul-sifier for petroleum emulsions of the water-in-oil type, or oil-in-water type, or in the prevention of corrosion of metallic surfaces, particularly ferrous surfaces, or as. anasphalt additive for anti-stripping purposes.

In light of 'what has been said, 'and'the simplicity of salt formation, it does not appear that any illustration is required. However, before referring to Table III which follows immediately hereafter, reference is made to Ex- 12 exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000

or l to 20,000, or 1 to 30,000, or even 1 to40,000, or '1' j to 50,000 as in desalting practice, such an apparent inample 1 solubility in oil and water is not significant because said Example reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the ma- This Salt was made from condensate Example 1b terlal or materials employed as the demulsifying agent Example 1b in turn was madefrom resin 2a and diethof my f f ylamine. 882 grams of the resin dissolved in an equal In pr actlcmg F presellt P thefreatmg weight of xylene were reacted with 145 grams or diethmulslfymg agent 18 used the conventwnal Wjcll ylamine and 162 grams of 37% formaldehyde. All this known to the art, descnbed for example, In Patent has been described previously. 'The weight of the con- 216264929 dated January 5 Part and 1'efe1"ence dens-ate on a 1 t f basis was 0 grams This 1s made thereto for a description of conventional prorepresented approximately, 27 grams of basic nitr0 cedures of demulsifying, including batch, continuous, and j gen. To this mixture, with constant stirring, there was f f' de'mulslficatlon the [P essellllallX added 780 grams of 50% gluconic acid and Stirring volving lntroduclng a small amount of demulslfier 111110 continued for one hour. The solution was poured into a large amount of 31110151911 Wlth adequate adII 11XtuI'e aseparatory funnel, or syphon arrangement, and allowed 20. w1th or wlthout the applrcatlon of heat, and allowlng the to stand at 40 C. for 3'days. A slight amount ofaque- IIllXtufe t0 stfatlfyous layer separated out at the bottom. Enough propyl AS noted abPVe, the Products hel'ell'l descl'lbed maybe alcohol, somewhat less than 100 grams, wa dded t used not only in dlluted form, but also may be used adbring the final Weight to 2884 grams thus representing apmixed with some other chemical demulslfier. A mixture proximately at solution. which illustrates such combmation is the following:

A number of other examples are included in Table 0 Glucon'i-c acid salt, for example, the product of Ex- III, following: ample 1c, 20%;

TABLE I11 Condensate in turn derived from Salt formation Salt 1t fr Wt. of Final 0 1 e Amt. 37% eonden- Theo. 50% wt. ad- No. den- Resin Amt. sol- Amine rmsate on basic glujusted to sate No. resin, Solvent vent, Amino used used, aldesolventnitroconic approx. N0 gms, gms. gms. hyde, free gen, acid, 50% salt,

gins. basis, gms. gms. 50% solv., gms. gms.

882 Xylene" 882 Diethylamine 146 162 1,052 27.8 780 2,884 480 do 480 do 73 81 505 13.9 390 1,520 633 .do- 633 o 73 718 13.9 390 1,826 441 do 441 D1butylam1ue. 129 81 582 14.0 390 1,554 480 do 480 do 129 81 021 14.0 390 1,632 033 do 633 do.. 129 81 774 14.0 390 1,938 882 do. 882 Morphol'me. 174 102 1,080 23.0 780 2,940 480 do. 480 0' 87 81 579 14.0 390 1,548 633 ...do.... 033 0.05 s7 81 732 14.0 390 1,854 473 'do.l 473 Dioctylalnine. 117 100 002 6.8 1,394 511 do 511 do 117 100 040 6.8 190 1,470 051 do 665 117 81 794' 6.8 190 1,778 882 '...do. 882 Diethylamiuc-.. 140 162 1,052 27.8 390 2,494 441 do 441 Dibutylamine... 129 81 582 14.0 1, 359 '882 do 882 Morpholine 174 162 1,020 28.0 390 2, 430

PART. 6 A cyclohexylamine salt of a polypropylated naphthalene I Conventional demulsifying agents employed the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene,

tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl. alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained It is well known that conventional demulsifying agents may be used inaWater-soluble form, orin an oil-soluble form, min a form exhibiting both oilandwater-s olu' bility. Sometimes they may be used in a form" which monosulfonic acid, 24%; 1

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sul- .water-in-oil type characterized by subjecting the emulsion to the action of a clemulsifier including the gluconic. acid salts of the basic products obtained in turn in the process of condensing (a). an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low stage phenolaldehyde resin having an aver age molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard to methylol-forrning reactivity;

said resin being derived by reaction between a difunctional monohydri'c phenol and an aldehyde having not.

over 8 carbon atoms and reactive toward said phenol; said 13" resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an 'oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde'resin havingan average molecular weight corresponding to at least 3 and \not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction bet-ween a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said-resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with theadded proviso that the condensation reaction be conducted soasv to produce a significant portion of the resultant. in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heatstable.

3. A process for breaking petroleum-emulsions of the.

Water-in-oil type characterized by subjecting'the emulsion to the action of a demulsifier including the gluconic acidsalts of the basic products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible,

non-oxygenated organic solvent-soluble, water-insoluble,

low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula.

14;, in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon' atoms in any group attached to the amino nitrogen atom;

and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule" by virtue of a formaldehyde-derived methylene bridge 1 connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable;

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in, the process of condensing (a) an oxyalkylation-susceptible,

fusible, non-oxygenated organic solvent-soluble, water insoluble, low-stage phenol-aldehyde resin having an av-J erage molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde'hav ing not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monamine having not more than 32, carbon atoms in any group attached to the amino nitrogen atom,

and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three ,reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the molar vratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the. process be heat-stable;

5. A process for breaking petroleum emulsions of the I water-in-oil type characterized by subjecting the emulnot over 6 phenolic nuclei resin molecule; said resin being I difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula V 15" in which R is'an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom,

and formaldehyde; said condensation reaction being conducted'at a temperature sufi'lciently high to eliminate waterand below the pyrolytic point of the reactants and resultants of, reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge.

the water-in-oil type characterized bysubjecting the emult sion to the action of a demulsifier including the gluconic acid salts of the'basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsolub'le, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and form'aldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substi-' tuted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, witht the proviso that the conden: sation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

7. A process for breaking petroleum emulsions of the Water-in-oi'l type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, 'waterinsoluble, low-stage phenol-formaldehyde resin'having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in thesubstantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufilciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2,respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

8. A process for breaking petroleum emulsions of the water-imoil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible,

non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei perresin nrolecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in 'which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having no more than 32 carbon atoms in any group attached to 'the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that'said procedure involve the use of a solvent; and with the [final proviso that the resinous condensation product resulting from the process be heatstalble. e

9. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion tional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the para position; (b) -a basic non-hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the con densation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be beatstable.

10. The process of claim 1 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

11. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 3 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient 18 to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 4 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal Weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

14. The process of claim 5 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 6 with the proviso that the hydrophile properties of the gluconic acid salt of thebasic product in an'equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 7 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 8 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 9 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS 2,031,557 Bruson Feb. 18, 1936 2,457,634 Bond et al. Dec. 28, 1948 2,535,380 Adams et al. Dec. 26, 1950 2,542,001 De Groote et a1. Feb. 20, 1951 2,545,692 Gleim Mar. 20, 1951 2,568,739 Kirkpatrick et al. Sept. 25, 1951 2,679,484 De Groote May 25, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, LOW STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 